Method of treating hydrocarbons



Patented June 18,1940 l 'l UNITED STATES PATENT OFFICE 2,204,673 METHOD OF TREATING HYDBOCARBONS 4 Stewart 0. Fulton, Elizabeth, N. 1., and Thomas Cross, .Jr., Baton Rouge, La.,' minors to Standard Oil Development Company, a corpo- 1 ration of Delaware No Drawing. Application December 19, 1935, Serial No. 55,234

1 Claim. (Cl. 196-10) This invention relates to novel methods of Example 3 treating hydrocarbons'such as by polymerization, Another polymerization run was made Similar gi t m to Example 2, except that the catalyst was actima consls S m suppo ng vated with hydrogen chloride. It was found that normally easily volatihzable metal halide catathe polymerization rate of Example 2 could be particplany aluminum Chlorideon an active maintained for longer periods. Removal of the silica gel base in the form of lumps, pills, etc., hydrogen chloride caused a gradual drop in p1y then using that catalysfi efiectmg're' mer production which, on reintroducing the hyactions, such as the polymerization of normally drogen chloride agammcr-eased gaseous olefines, e. g., ethylene, propylene, and

various butenes, into liquids of the gasoline boil- Ewample 4 ing range, or the cracking of or reforming of normally liquid hydrocarbon fractions, either to produce lower boiling liquids, or to produce liquid fractions having improved properties, such as higher octane number for motor fuel use.

The invention will be thoroughly understood from the following examples, which are given for the sake of illustration only, and from the subsequent description. Emample 5 An East Texas heavy naphtha was passed over a catalyst, prepared as in Example 1, and maintained atabout ZOO-230 C. The liquidproduct showed an octane number improvement of 9.0 16 (,C. F. R. method), and 2.9% gas was obtained, which consists mainly of isobutane (no unsaturates) as shown by analyses.

Example 1 The procedure of Example 4 was repeated except that the reaction temperature was maintained at 300350 0., resulting in the production of a lighter gas, a 4% gas loss being obtained for the same octane number improvement as obtained in Example 4. The catalyst still retained ample aluminum chloride at these higher temperatures (SOD-350 C.) to be highly active.

Instead of using the specially prepared silica gel described above as the support, other suitable 3o materials may be used. such as activated alumina, although silica gel specially prepared as in Ex- As one example. of a suitable method of .pre-. paring the catalyst, the following explanation is given: An aqueous solution of sodium silicate is treated with hydrochloric acid to form a precipitate of silica acid gel, which is then freed from chlorides according to the usual methods (washing with water). The resulting gel is dried, com pressed into pill form and heated to exactly the temperature to be used in the polymerization, cracking, or other treating processes and cooled to atmospheric temperature. 2 grams of aluminum ample 1 is preferred It is believed that the chloride are then dissolved in 50 cc. of ethylene aluminum chloride forms a molecular complex dichloride and the solution is poured over 22 with the silica geL grams of the Slhca gel m h rfaactor chamber Also, although aluminum chloride is preferred, (to be for the l l The other normally solid but easily volatilizable metal then heated while passing a Stream of halides may be used, for example, ferric chloride. dry nitrogen through it, whereby the s It is not intended that the invention be limited (ethylene.dlch1nde.) recovergd and any by any of the examples given, nor by any theories cess aluminum chloride not held in the gel strucsuggested for the operation of the invention, but

is Y when the reactqr reachesthe only by the appended claim in .which it is intended deslred reaction temperature the mtrogen flow to claim all novelty inherent in the invention as stopped and the catalyst is ready for .use. broadly as the prior art permits Exa7nple 2 We claim: I 45 The process of polymenzing normally gaseous, 21 liters Der hour of a petroleum refi y C4 hydrocarbons containing olefins which comprises (butane) cut in gaseous form, which contains a contacting them at a temperature between 200 substantial amount of butenes (38.5%), was fed t 300 t catalyst prepared by jmpregover 22 g ams of a Catalyst, P p s nating activated silica gel with aluminum chlo- 50 scribed i E p e 1, and maintained at a ride dissolved in ethylene dichloride and heating Derature Of About grams p the mass at a temperature suificient to drive oil hour of liquid polymer in the gasoline range were t ethylene dichloride. I obtained in the first 2 hours. This amounted to STEWART C. FULTON.

conversion of about 37.0%. THOMAS CROSS. Jr. II 

